JP2015214646A - Curable epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable epoxy resin composition capable of forming a cured product which has excellent durability against high-temperature heat or thermal shock and high adhesiveness or adhesive strength to an adherend and can particularly improve conduction characteristics, moisture absorption reflow resistance and thermal shock resistance of an optical semiconductor device at a high temperature by using as a sealing material of an optical semiconductor element.SOLUTION: A curable epoxy resin composition comprises (A) an alicyclic epoxy compound, (B) an oxetane compound having one or more oxetane rings in the molecule, (C) a polyvinyl butyral resin and (D) at least one antioxidant selected from the group consisting of a phosphorus-based antioxidant and a phenol-based antioxidant.

Description

  The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, and an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition. About.

  In recent years, the output of optical semiconductor devices has been increased, and high heat resistance and light resistance are required for a resin (encapsulant) that covers an optical semiconductor element in such an optical semiconductor device. Conventionally, as a sealing agent for forming a sealing material having high heat resistance, for example, a composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin is known (see Patent Document 1). However, when the composition is used as a sealing agent for a high-power blue / white light semiconductor, the coloring of the sealing material proceeds due to the heat emitted from the optical semiconductor element, and the light that should originally be output As a result, the light intensity of the light output from the optical semiconductor device is reduced over time.

  3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4 as a sealing agent that forms a cured product (sealing material) that has high heat resistance and light resistance and is not easily yellowed -Liquid alicyclic epoxy resins having an alicyclic skeleton such as an adduct of epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and ε-caprolactone, 1,2,8,9-diepoxylimonene, etc. are known. ing. However, the cured products of these alicyclic epoxy resins are susceptible to various stresses, and cracks are generated when a thermal shock such as a cooling cycle (repeating heating and cooling periodically) is applied. Etc. had occurred.

  In addition, an optical semiconductor device (for example, a surface-mount type optical semiconductor device) generally undergoes a reflow process for bonding an electrode of the optical semiconductor device to a wiring board by soldering. In recent years, lead-free solder having a high melting point has been used as a solder as a bonding material, and heat treatment in a reflow process has become a higher temperature (for example, a peak temperature of 240 to 260 ° C.). . Under such circumstances, in the conventional optical semiconductor device, there is a problem of deterioration such that the sealing material is peeled off from the lead frame of the optical semiconductor device due to the heat treatment in the reflow process, or the sealing material is cracked. Has occurred.

  For this reason, the sealing material in the optical semiconductor device has high heat resistance and light resistance, and also has a characteristic that cracks are not easily generated when a thermal shock is applied (sometimes referred to as “thermal shock resistance”), and Further, there is a demand for characteristics in which cracks and peeling are unlikely to occur even when heat treatment is performed in the reflow process. In particular, in recent years, from the viewpoint of ensuring higher reliability of the sealing material, the optical semiconductor device is kept under high humidity conditions for a certain time (for example, 192 hours under conditions of 30 ° C. and 60% RH; 60 ° C., 60% RH 52 hours under conditions of 85 ° C., 168 hours under conditions of 60% RH), and even when heat-treated in the reflow process after absorbing moisture, the above-mentioned cracks and peeling are unlikely to occur (such as The characteristic is sometimes called “moisture absorption reflow resistance”.

JP 2000-344867 A

Accordingly, an object of the present invention is to have excellent durability against high-temperature heat and thermal shock, high adhesion to an adherend and high adhesive strength, and particularly when used as a sealing material for an optical semiconductor element, the optical semiconductor device has a high temperature. An object of the present invention is to provide a curable epoxy resin composition capable of forming a cured product capable of improving current-carrying characteristics, moisture absorption reflow resistance, and thermal shock resistance.
Another object of the present invention is to provide an optical semiconductor device that is excellent in durability against high-temperature heat and thermal shock, has high adhesion to an adherend and high adhesive strength, and is used as a sealing material for optical semiconductor elements. An object of the present invention is to provide a cured product capable of improving current-carrying characteristics at high temperatures, moisture absorption reflow resistance, and thermal shock resistance.
Furthermore, another object of the present invention is to provide an optical semiconductor device having excellent durability and quality that is excellent in energization characteristics at high temperatures, moisture absorption reflow resistance, and thermal shock resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable epoxy resin composition containing an alicyclic epoxy compound, an oxetane compound, a polyvinyl butyral resin, and a specific antioxidant as essential components. Excellent durability against high temperature heat and thermal shock, high adhesion and adhesion strength to adherend, especially when used as a sealing material for optical semiconductor elements, high temperature current characteristics of optical semiconductor devices, moisture absorption reflow resistance The present invention was completed by finding that a cured product capable of improving the property and thermal shock resistance can be formed.

  That is, the present invention relates to an alicyclic epoxy compound (A), an oxetane compound (B) having one or more oxetane rings in the molecule, a polyvinyl butyral resin (C), a phosphorus antioxidant and a phenolic compound. There is provided a curable epoxy resin composition comprising at least one antioxidant (D) selected from the group consisting of antioxidants.

  Furthermore, the said curable epoxy resin composition whose oxetane compound (B) is an oxetane compound (B1) which has a 1 or more hydroxyl group in a molecule | numerator is provided.

  Furthermore, the said curable epoxy resin composition containing the isocyanuric acid derivative (E) which has a 1 or more oxirane ring in a molecule | numerator is provided.

  Furthermore, the said curable epoxy resin composition containing a curing catalyst (F) is provided.

  Furthermore, the said curable epoxy resin composition containing a hardening | curing agent (G) and a hardening accelerator (H) is provided.

  The present invention also provides a cured product obtained by curing the curable epoxy resin composition.

  Furthermore, the said curable epoxy resin composition which is a resin composition for optical semiconductor sealing is provided.

  Moreover, this invention provides the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the said curable epoxy resin composition.

  Since the curable epoxy resin composition of the present invention has the above-described configuration, it is excellent in durability against high-temperature heat and thermal shock by being cured (for example, even when high-temperature heat or thermal shock is applied). It is possible to form a cured product having high adhesion to the adherend and high adhesive strength. For this reason, when the curable epoxy resin composition of the present invention is used as a resin composition for encapsulating an optical semiconductor in particular, current-carrying characteristics at high temperatures such as low light intensity hardly occur under severe conditions of high temperature and long time. In addition, even when thermal shock such as high temperature heat or cooling cycle is applied in the reflow process (especially the reflow process after moisture absorption), there are problems such as cracking / peeling of the sealing material and non-lighting of the optical semiconductor device. It is possible to obtain an optical semiconductor device excellent in moisture absorption reflow resistance and thermal shock resistance and excellent in quality and durability.

It is the schematic which shows one Embodiment of the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the curable epoxy resin composition of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. It is an example of the surface temperature profile (temperature profile in one heat processing among two heat processing) of the optical semiconductor device in the solder heat resistance test of an Example.

<Curable epoxy resin composition>
The curable epoxy resin composition of the present invention includes an alicyclic epoxy compound (A) and an oxetane compound (B) having one or more oxetane rings in the molecule (sometimes simply referred to as “oxetane compound (B)”). And at least one antioxidant (D) selected from the group consisting of a phosphorus butyral resin (C), a phosphorus antioxidant and a phenolic antioxidant (simply "antioxidant (D)"). Is a composition (curable composition) containing as an essential component. The curable epoxy resin composition of the present invention may contain any component other than these essential components (for example, an isocyanuric acid derivative (E) described later).

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group (oxiranyl group) in the molecule (in one molecule). . As the alicyclic epoxy compound (A), specifically, (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, (Ii) A compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and the like.

  The compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (i) is arbitrarily selected from known or commonly used compounds. Can be used. Especially, as said alicyclic epoxy group, a cyclohexene oxide group is preferable.

As the compound (i) having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, a compound having a cyclohexene oxide group is preferable from the viewpoint of transparency and heat resistance. In particular, a compound (alicyclic epoxy compound) represented by the following formula (I) is preferable.

  In the above formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include divalent hydrocarbon groups, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected.

  Examples of the compound in which X in the above formula (I) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane and the like.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

  The linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation. An alkenylene group; a group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include those exemplified above.

Representative examples of the compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10). In the following formulas (I-5) and (I-7), l and m each represent an integer of 1 to 30. R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene. And linear or branched alkylene groups such as a group, a heptylene group, and an octylene group. Among these, C1-C3 linear or branched alkylene groups, such as a methylene group, ethylene group, a propylene group, an isopropylene group, are preferable. N1 to n6 in the following formulas (I-9) and (I-10) each represent an integer of 1 to 30.

  In addition to the compounds described above, examples of the compound represented by the formula (I) include bis (3,4-epoxycyclohexylmethyl) ether, 1,2-bis (3,4-epoxycyclohexyl) ethane, , 2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane and the like.

Examples of the compound (ii) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).

In the formula (II), R ′ is a group (p-valent organic group) obtained by removing p hydroxyl groups (—OH) from a p-valent alcohol in the structural formula, and p and n each represent a natural number. Examples of the p-valent alcohol [R ′ (OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (II) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

  In the curable epoxy resin composition of the present invention, the alicyclic epoxy compound (A) can be used alone or in combination of two or more. In addition, as the alicyclic epoxy compound (A), for example, commercially available products such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) may be used.

  As the alicyclic epoxy compound (A), a compound represented by the above formula (I-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; for example, trade name “Celoxide 2021P” (Daicel Co., Ltd.) etc. are particularly preferred.

  The content (blending amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is 15 with respect to the total amount (100% by weight) of the curable epoxy resin composition. -90 weight% is preferable, More preferably, it is 20-85 weight%, More preferably, it is 25-80 weight%. By controlling the content of the alicyclic epoxy compound (A) within the above range, the curability of the curable epoxy resin composition is further improved, and the heat resistance, light resistance, and mechanical strength of the cured product are further improved. Tend.

  In the curable epoxy resin composition of the present invention, the alicyclic compound with respect to the total amount (100% by weight) of the alicyclic epoxy compound (A), the oxetane compound (B), the polyvinyl butyral resin (C), and the isocyanuric acid derivative (E). Although the ratio of a formula epoxy compound (A) is not specifically limited, 40 to 90 weight% is preferable, More preferably, it is 45 to 85 weight%, More preferably, it is 50 to 80 weight%. By setting the ratio of the alicyclic epoxy compound (A) to 40% by weight or more, the curability of the curable epoxy resin composition tends to be further improved, and the heat resistance and light resistance of the cured product tend to be further improved. . On the other hand, when the ratio of the alicyclic epoxy compound (A) is 90% by weight or less, the thermal shock resistance of the cured product tends to be further improved.

[Oxetane compound (B)]
The oxetane compound (B) in the curable epoxy resin composition of the present invention is a compound having one or more oxetane rings in the molecule. By including the oxetane compound (B) in the curable epoxy resin composition of the present invention, an optical semiconductor device having mainly improved durability against thermal shock (such as crack resistance) of the cured product and excellent thermal shock resistance. Is obtained. The number of oxetane rings in the molecule of the oxetane compound (B) is not particularly limited as long as it is 1 or more, but 1 to 6 is preferable from the viewpoint of durability (crack resistance, etc.) of the cured product, More preferably, it is 1-4.

  As the oxetane compound (B), known or commonly used oxetane compounds can be used, and are not particularly limited. For example, oxetane compounds described in JP-A-11-302372 and JP-A-2004-143252 are used. Can be used. Specifically, for example, 3,3-bis (vinyloxymethyl) oxetane, 3-methyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl- 3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3,3 -Bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, 4,4'-bis [(3-Ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [(3-ethyl-3-oxetani ) Methoxymethyl] cyclohexane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3-{[(3-ethyloxetan-3-yl) methoxy] methyl} And oxetane.

  Among them, the oxetane compound (B) is sometimes referred to as a compound having one or more hydroxyl groups in the molecule (“oxetane compound (B1)” in terms of further improving the adhesion and thermal shock resistance of the cured product. A compound having one or more oxetane rings and one or more hydroxyl groups in the molecule) is preferred. The number of hydroxyl groups in the molecule of the oxetane compound (B1) is not particularly limited as long as it is 1 or more, but 1 to 6 is preferable from the viewpoint of adhesion of the cured product and thermal shock resistance, and more preferably. 1 to 4 pieces. Examples of the oxetane compound (B1) include 3-ethyl-3- (hydroxymethyl) oxetane and 3-methyl-3- (hydroxymethyl) oxetane.

  In the curable epoxy resin composition of the present invention, one oxetane compound (B) can be used alone, or two or more oxetane compounds (B) can be used in combination. In addition, a commercial item can also be used as an oxetane compound (B), As such a commercial item, brand name "Aron oxetane OXT-101", "Aron oxetane OXT-221" (above, Toagosei ( Etc.).

  Although content (blending amount) of the oxetane compound (B) in the curable epoxy resin composition of the present invention is not particularly limited, it is 10 to 150 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). More preferably, it is 15-100 weight part, More preferably, it is 20-80 weight part. By setting the content of the oxetane compound (B) to 10 parts by weight or more, the adhesion of the cured product to the adherend and the durability against thermal shock tend to be further improved. On the other hand, when the content of the oxetane compound (B) is 150 parts by weight or less, the transparency, heat resistance, and light resistance of the cured product tend to be further improved.

[Polyvinyl butyral resin (C)]
The polyvinyl butyral resin (C) in the curable epoxy resin composition of the present invention is obtained by acetalization (butyralization) by reacting polyvinyl alcohol with butyraldehyde. When the curable epoxy resin composition of the present invention contains the polyvinyl butyral resin (C), mainly, the adhesion and moisture and air tightness of the cured product are improved, and the moisture absorption reflow resistance of the optical semiconductor device is further improved. Furthermore, for example, compared with the case where a polyvinyl formal resin is used instead of the polyvinyl butyral resin (C), a cured product having less coloring and excellent transparency can be obtained. In particular, when the polyvinyl butyral resin (C) is used in combination with the oxetane compound (B) and the antioxidant (D), the thermal shock resistance and moisture absorption reflow resistance of the optical semiconductor device are compatible at a very high level.

  The degree of butyralization of the polyvinyl butyral resin (C) is not particularly limited, but is preferably 50 to 85 mol%, more preferably 60 to 80 mol%, and still more preferably 65 to 75 mol%. By using the polyvinyl butyral resin (C) in which the degree of butyralization is controlled within the above range, there is a tendency that the adhesion and moisture-tightness of the cured product are further improved and the moisture absorption reflow resistance of the optical semiconductor device is further improved. is there. The degree of butyralization is the butyral monomer unit (corresponding to the structure in which vinyl alcohol is polymerized) with respect to the total amount (100 mol%) of the monomer units constituting the polyvinyl butyral resin (C). Monomer unit).

  The polyvinyl butyral resin (C) usually has monomer units corresponding to a structure in which vinyl alcohol is polymerized. The ratio of the monomer units corresponding to the structure in which vinyl alcohol is polymerized with respect to the total amount (100 mol%) of the monomer units constituting the polyvinyl butyral resin (C) is not particularly limited, but is preferably 10 to 40 mol%, more preferably. Is 15 to 38 mol%, more preferably 20 to 35 mol%. By using the polyvinyl butyral resin (C) in which the above ratio is controlled in such a range, the adhesiveness and moisture and airtightness of the cured product are further improved, and the moisture absorption reflow resistance of the optical semiconductor device is further improved. There is.

  The polyvinyl butyral resin (C) may have a monomer unit corresponding to a structure in which vinyl acetate is polymerized. The ratio of the monomer unit corresponding to the structure in which vinyl acetate is polymerized with respect to the total amount (100 mol%) of the monomer units constituting the polyvinyl butyral resin (C) is not particularly limited, but is usually 5 mol% or less (for example, 0 ~ 3 mol%). The polyvinyl butyral resin (C) has a monomer unit corresponding to a structure obtained by polymerizing butyral monomer units and vinyl alcohol, and the remaining monomer units are monomer units corresponding to a structure obtained by polymerizing vinyl acetate. Some are preferred. Examples of such a polyvinyl butyral resin (C) include 50 to 80 mol% of butyral monomer units with respect to the total amount (100 mol%) of monomer units constituting the polyvinyl butyral resin (C), vinyl A monomer unit corresponding to a structure in which alcohol is polymerized is 10 to 50 mol%, and the remainder is a monomer unit corresponding to a structure in which vinyl acetate is polymerized.

  Although the weight average molecular weight of polyvinyl butyral resin (C) is not specifically limited, 500-200000 are preferable, More preferably, it is 3000-14000, More preferably, it is 10,000-100000, Most preferably, it is 15000-70000. By using the polyvinyl butyral resin (C) whose weight average molecular weight is controlled within the above range, the adhesion of the cured product and the moisture and air tightness are further improved, and the moisture absorption and reflow resistance of the optical semiconductor device tends to be further improved. is there. On the other hand, when the weight average molecular weight of the polyvinyl butyral resin (C) is too large (for example, exceeding 200,000), the compatibility with other components in the curable epoxy resin composition is lowered, and the physical properties of the cured product are adversely affected. May reach.

  In the curable epoxy resin composition of the present invention, the polyvinyl butyral resin (C) can be used singly or in combination of two or more. The polyvinyl butyral resin (C) can be produced by a known or conventional method. For example, the polyvinyl butyral resin (C) is obtained by a method of acetalizing by reacting polyvinyl alcohol with butyraldehyde in the presence of an acid catalyst. Examples of the polyvinyl butyral resin (C) include, for example, a trade name “ESREC B” series (manufactured by Sekisui Chemical Co., Ltd.), a trade name “Mobital B” series, and a “Pioloform” series (manufactured by Kuraray Co., Ltd.). Commercial products such as these can also be used.

  The content (blending amount) of the polyvinyl butyral resin (C) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount (total content) of the alicyclic epoxy compound (A) and the oxetane compound (B). 1) to 30 parts by weight with respect to 100 parts by weight, more preferably 3 to 25 parts by weight, and still more preferably 5 to 20 parts by weight. By setting the content of the polyvinyl butyral resin (C) to 1 part by weight or more, there is a tendency that the adhesiveness and moisture-tightness of the cured product are further improved, and the moisture absorption reflow resistance of the optical semiconductor device is further improved. On the other hand, by setting the content of the polyvinyl butyral resin (C) to 30 parts by weight or less, durability against thermal shock of the cured product is further improved, and thermal shock resistance of the optical semiconductor device tends to be further improved.

[Antioxidant (D)]
The antioxidant (D) in the curable epoxy resin composition of the present invention is at least one antioxidant selected from the group consisting of phosphorus antioxidants and phenolic antioxidants. By including the antioxidant (D) which is a specific antioxidant, the curable epoxy resin composition of the present invention mainly deteriorates the components of the curable epoxy resin composition, in particular, polyvinyl butyral (C). Is suppressed, and the current-carrying characteristics and moisture absorption reflow resistance at high temperatures of the optical semiconductor device are improved.

  As phosphorus antioxidant as antioxidant (D), the well-known thru | or usual phosphorus compound used as antioxidant can be used, Although it does not specifically limit, For example, a triphenyl phosphite, diphenyl Isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) Phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butyl-4-methylphenyl) phosphite Bis [2-t-butyl-6-methyl Phosphites such as -4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3 And oxaphosphaphenanthrene oxides such as 5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. In addition, a phosphorus antioxidant can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  As the phenolic antioxidant as the antioxidant (D), a known or conventional phenolic compound used as an antioxidant can be used, and is not particularly limited. For example, 2,6-di- t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc. Monophenols of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3- Methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl Bisphenols such as 2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane; 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-) 3′-tert-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) -s-triazine-2,4 - (1H, 3H, 5H) trione, polymer type phenol such as tocopherol and the like. In addition, a phenolic antioxidant can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  In addition, in the curable epoxy resin composition of this invention, antioxidant (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type. The antioxidant (D) can also be produced by a known or conventional method. For example, the trade name “IRGANOX1010” (manufactured by BASF, a phenolic compound), the trade name “IRGAFOS168” (manufactured by BASF, a phosphorous compound) ) Etc. can also be used.

  Among these, the curable epoxy resin composition of the present invention is a phosphorous antioxidant and a phenolic antioxidant as the antioxidant (D), particularly from the viewpoint of current-carrying characteristics at high temperatures of the optical semiconductor device and moisture absorption reflow resistance. It is preferable that both are included.

  Although content (blending amount) of the antioxidant (D) in the curable epoxy resin composition of the present invention is not particularly limited, the total amount of the polyvinyl butyral resin (C) contained in the curable epoxy resin composition is 100 parts by weight. The amount is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, and still more preferably 0.5 to 5 parts by weight. Since the deterioration of the polyvinyl butyral resin (C) is more efficiently suppressed by setting the content of the antioxidant (D) to 0.1 parts by weight or more, a cured product (sealing material) for the adherend. There is a tendency that the adhesiveness and adhesive strength of the optical semiconductor device become higher, and the moisture absorption reflow resistance of the optical semiconductor device further improves. On the other hand, when the content of the antioxidant (D) is 10 parts by weight or less, a cured product having a better hue tends to be obtained.

  When the curable epoxy resin composition of the present invention contains both a phosphorus antioxidant and a phenolic antioxidant as the antioxidant (D), these proportions [phosphorus antioxidant / phenolic antioxidant] Although (weight ratio) is not specifically limited, 10 / 90-90 / 10 are preferable, More preferably, it is 25 / 75-75 / 25, More preferably, it is 40 / 60-60 / 40. Since the deterioration of the polyvinyl butyral resin (C) is more efficiently suppressed by controlling the ratio of the phosphorus-based antioxidant and the phenol-based antioxidant to the above range, a cured product (sealing material) for the adherend ) And the adhesive strength, the moisture absorption reflow resistance of the optical semiconductor device tends to be further improved.

[Isocyanuric acid derivative (E)]
The curable epoxy resin composition of the present invention further contains an isocyanuric acid derivative (E) having one or more oxirane rings in the molecule (sometimes simply referred to as “isocyanuric acid derivative (E)”). Also good. The isocyanuric acid derivative (E) is a derivative of isocyanuric acid and has one or more oxirane rings in the molecule. When the curable epoxy resin composition of the present invention contains the isocyanuric acid derivative (E), the adhesion of the cured product to the adherend, the adhesive strength, and the durability against thermal shock are improved, and the thermal shock resistance of the optical semiconductor device. There is a tendency to improve further. The number of oxirane rings in the molecule of the isocyanuric acid derivative (E) may be one or more, and is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

As an isocyanuric acid derivative (E), the compound represented by following formula (1) is mentioned, for example.

In the formula (1), R ^X , R ^Y , and R ^Z (R ^{X to} R ^Z ) are the same or different and represent a hydrogen atom or a monovalent organic group. However, at least one of R ^{X to} R ^Z is a monovalent organic group containing an oxirane ring. Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group); a monovalent aromatic hydrocarbon group (for example, an aryl group); A cyclic group; a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The monovalent organic group may be a group having a substituent (for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom). Examples of the monovalent organic group containing an oxirane ring include groups having an oxirane ring such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group, and a cyclohexene oxide group.

More specifically, as the isocyanuric acid derivative (E), a compound represented by the following formula (1-1) (monoallyl diglycidyl isocyanurate compound), a compound represented by the following formula (1-2) ( Diallyl monoglycidyl isocyanurate compound), a compound represented by the following formula (1-3) (triglycidyl isocyanurate compound), and the like.

In the above formula (1-1), formula (1-2), and formula (1-3) (formulas (1-1) to (1-3)), R ¹ and R ² are the same or different, A hydrogen atom or an alkyl group having 1 to 8 carbon atoms is shown. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and octyl groups. Examples thereof include a chain or branched alkyl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable. R ¹ and R ² in the above formulas (1-1) to (1-3) are particularly preferably hydrogen atoms.

  Representative examples of the compound represented by the above formula (1-1) include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2 -Methylpropenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate and the like.

  Representative examples of the compound represented by the formula (1-2) include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3-bis ( 2-methylpropenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5- (2-methylepoxypropyl) isocyanurate and the like.

  Typical examples of the compound represented by the above formula (1-3) include triglycidyl isocyanurate, tris (2-methylepoxypropyl) isocyanurate, and the like.

  The isocyanuric acid derivative (E) may be modified in advance by adding a compound that reacts with an oxirane ring such as alcohol or acid anhydride.

  Among these, as the isocyanuric acid derivative (E), compounds represented by the above formulas (1-1) to (1-3) are preferable from the viewpoint of heat resistance and thermal shock resistance of the cured product, and more preferably the above formula. It is a compound represented by (1-1). In the curable epoxy resin composition of the present invention, the isocyanuric acid derivative (E) may be used alone or in combination of two or more. Examples of the isocyanuric acid derivative (E) include, for example, trade name “TEPIC” (manufactured by Nissan Chemical Industries, Ltd.); trade names “MA-DGIC”, “DA-MGIC” (above, Shikoku Kasei Kogyo Co., Ltd.) (Commercially available) can also be used.

  Although content (blending amount) of the isocyanuric acid derivative (E) in the curable epoxy resin composition of the present invention is not particularly limited, it is 5 to 100 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). Is preferable, more preferably 8 to 60 parts by weight, still more preferably 10 to 30 parts by weight. By setting the content of the isocyanuric acid derivative (E) to 5 parts by weight or more, adhesion of the cured product to an adherend such as an electrode and durability against thermal shock tend to be further improved. On the other hand, if the content of the isocyanuric acid derivative (E) exceeds 100 parts by weight, the solubility of the isocyanuric acid derivative (E) in the curable epoxy resin composition is lowered, and the physical properties of the cured product may be adversely affected. .

  The total amount (total content) of the alicyclic epoxy compound (A), oxetane compound (B), and isocyanuric acid derivative (E) contained in the curable epoxy resin composition of the present invention is not particularly limited, but is curable. 70 wt% or more (for example, 70 to 100 wt%) is preferable with respect to the total amount (100 wt%) of the cationically polymerizable compound contained in the epoxy resin composition, more preferably 80 wt% or more, and still more preferably 90 wt%. % By weight or more. By controlling the total amount of the alicyclic epoxy compound (A), the oxetane compound (B), and the isocyanuric acid derivative (E) to the above ranges, the thermal shock resistance and moisture absorption reflow resistance were compatible at a very high level. There is a tendency to obtain an optical semiconductor device.

[Curing catalyst (F)]
The curable epoxy resin composition of the present invention may contain a curing catalyst (F). The curing catalyst (F) starts and / or accelerates the curing reaction (polymerization reaction) of a cationically polymerizable compound such as an alicyclic epoxy compound (A), an oxetane compound (B), or an isocyanuric acid derivative (E). And a compound having a function of curing the curable epoxy resin composition. The curing catalyst (F) is not particularly limited. For example, a cationic polymerization initiator (photo cationic polymerization initiator, thermal cationic polymerization) that initiates polymerization by generating cationic species by performing light irradiation, heat treatment, or the like. Initiators, etc.), Lewis acid / amine complexes, Bronsted acid salts, imidazoles and the like.

  Examples of the photocationic polymerization initiator as the curing catalyst (F) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically. For example, triarylsulfonium hexafluorophosphate (for example, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate), sulfonium salt such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salt); diaryl iodonium hexafluorophosphate , Diaryl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodo Iodonium salts such as um [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; pyridinium salts such as N-hexylpyridinium tetrafluoroborate It is done. Moreover, as a photocationic polymerization initiator, for example, trade name “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, the United States) Commercial products such as Sartomer); trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.

  Examples of the thermal cationic polymerization initiator as the curing catalyst (F) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33”, “CP-66”. "CP-77" (manufactured by ADEKA); trade name "FC-509" (manufactured by 3M); trade name "UVE1014" (manufactured by GE); trade name "Sun-Aid SI-60L" “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-150L” (manufactured by Sanshin Chemical Industry Co., Ltd.); trade name “CG-24-61” ( Commercially available products such as BASF) can be preferably used. Further, as the thermal cationic polymerization initiator, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketone Examples thereof include a compound of a chelate compound with a phenol and a phenol such as bisphenol S.

As the Lewis acid / amine complex as the curing catalyst (F), a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited. For example, BF ₃ .n-hexylamine, BF ₃ · monoethylamine, BF ₃ · benzylamine, BF ₃ · diethylamine, BF ₃ · piperidine, BF ₃ · triethylamine, BF ₃ · aniline, BF ₄ - n-hexylamine, BF ₄ - monoethylamine, BF ₄ - benzylamine , BF ₄ · diethylamine, BF ₄ · piperidine, BF ₄ · triethylamine, BF ₄ · aniline, PF ₅ · ethylamine, PF ₅ · isopropylamine, PF ₅ · butylamine, PF ₅ · laurylamine, PF ₅ · benzylamine, AsF _5. Laurylamine etc. are mentioned.

  As the Bronsted acid salts as the curing catalyst (F), known or commonly used Bronsted acid salts can be used, and are not particularly limited. For example, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphoniums. Examples include salts.

  As the imidazoles as the curing catalyst (F), known or conventional imidazoles can be used, and are not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl Imidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4 - Mino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine, etc. Is mentioned.

  In the curable epoxy resin composition of the present invention, the curing catalyst (F) can be used singly or in combination of two or more. In addition, as above-mentioned, a commercial item can also be used as a curing catalyst (F).

  The content (blending amount) of the curing catalyst (F) in the curable epoxy resin composition of the present invention is not particularly limited, but is based on 100 parts by weight of the total amount of the cationic polymerizable compound contained in the curable epoxy resin composition. 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0.05 to 8 parts by weight. By using the curing catalyst (F) within the above range, the curing rate of the curable epoxy resin composition is increased, and the heat resistance and transparency of the cured product tend to be improved in a balanced manner.

[Curing agent (G)]
The curable epoxy resin composition of the present invention may contain a curing agent (G) instead of the curing catalyst (F), for example. The curing agent (G) is cured by reacting with a compound having a cyclic ether structure (oxirane ring or oxetane ring) such as an alicyclic epoxy compound (A), an oxetane compound (B), or an isocyanuric acid derivative (E). It is a compound which has the effect | action which hardens an adhesive epoxy resin composition. As the curing agent (G), a known or conventional curing agent can be used as a curing agent for an epoxy resin, and is not particularly limited. For example, acid anhydrides (acid anhydride curing agents), amines ( Amine curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, etc. Can be mentioned.

  As the acid anhydrides (acid anhydride curing agents) as the curing agent (G), known or commonly used acid anhydride curing agents can be used, and are not particularly limited. For example, methyltetrahydrophthalic anhydride (4 -Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride), dodecenyl succinic anhydride, methyl Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydrous Nadic acid, anhydrous methyl nadic acid, methyl hydride Dic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride Examples include acid copolymers and alkylstyrene-maleic anhydride copolymers. Among these, acid anhydrides [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] that are liquid at 25 ° C. are preferable from the viewpoint of handleability. On the other hand, for a solid acid anhydride at 25 ° C., for example, by dissolving in a liquid acid anhydride at 25 ° C. to form a liquid mixture, the curing agent (G ) Tends to be improved. As the acid anhydride curing agent, saturated monocyclic hydrocarbon dicarboxylic acid anhydrides (including those in which a substituent such as an alkyl group is bonded to the ring) are preferable from the viewpoint of heat resistance and transparency of the cured product.

  As the amines (amine-based curing agents) as the curing agent (G), known or conventional amine-based curing agents can be used, and are not particularly limited. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Aliphatic polyamines such as dipropylenediamine, diethylaminopropylamine, polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-amino Cycloaliphatic polyamines such as ethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; m-phenylenediamine, p-phenylenediamine, tri 2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6- Examples include mononuclear polyamines such as diamine, aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.

  As the phenols (phenolic curing agents) as the curing agent (G), known or conventional phenolic curing agents can be used, and are not particularly limited. For example, novolac-type phenol resins, novolac-type cresol resins, paraxylylene-modified phenols Examples thereof include aralkyl resins such as resins, paraxylylene / metaxylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.

  Examples of the polyamide resin as the curing agent (G) include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.

  As the imidazole (imidazole curing agent) as the curing agent (G), a known or commonly used imidazole curing agent can be used, and is not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanate Nu 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)] -Ethyl-s-triazine and the like.

  Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (G) include liquid polymercaptans and polysulfide resins.

  Examples of polycarboxylic acids as the curing agent (G) include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxy group-containing polyester, and the like.

  Among these, as the curing agent (G), acid anhydrides (acid anhydride curing agents) are preferable from the viewpoint of heat resistance and transparency of the cured product. In addition, in the curable epoxy resin composition of this invention, a hardening | curing agent (G) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Moreover, a commercial item can also be used as a hardening | curing agent (G). For example, as commercial products of acid anhydrides, trade names “Licacid MH-700” and “Licacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.); trade name “HN-5500” (Hitachi Chemical Industries) Etc.).

  Although content (blending amount) of the curing agent (G) in the curable epoxy resin composition of the present invention is not particularly limited, a compound having a cyclic ether structure contained in the curable epoxy resin composition (for example, alicyclic) 50-200 weight part is preferable with respect to 100 weight part of whole quantity of an epoxy compound (A), an oxetane compound (B), and an isocyanuric acid derivative (E)), More preferably, it is 80-150 weight part. More specifically, when acid anhydrides are used as the curing agent (G), 0. 0 per equivalent of cyclic ether in all compounds having a cyclic ether structure contained in the curable epoxy resin composition of the present invention. It is preferable to use it in the ratio which becomes 5-1.5 equivalent. By setting the content of the curing agent (G) to 50 parts by weight or more, curing can sufficiently proceed, and the toughness of the cured product tends to be further improved. On the other hand, by setting the content of the curing agent (G) to 200 parts by weight or less, coloring tends to be further suppressed and a cured product excellent in hue tends to be obtained.

[Curing accelerator (H)]
The curable epoxy resin composition of the present invention preferably further contains a curing accelerator (H), particularly when it contains the curing agent (G). The curing accelerator (H) is a compound having a function of accelerating the reaction rate when a compound having a cyclic ether structure reacts with the curing agent (G). The curing accelerator (H) may be a known or conventional curing accelerator, and is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, , Phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (for example, phenol Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, etc. Tertiary amines; Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Acid esters; phosphines such as triphenylphosphine and tris (dimethoxy) phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organometallic salts such as zinc octylate, tin octylate and zinc stearate; Examples thereof include metal chelates such as aluminum acetylacetone complex.

  In addition, a hardening accelerator (H) can also be used individually by 1 type in the curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type. Further, as the curing accelerator (H), trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “U-CAT 12XD” ( (Developed product) (San Apro Co., Ltd.); trade names "TPP-K", "TPP-MK" (Hokuko Chemical Co., Ltd.); trade name "PX-4ET" (Nippon Chemical Industry ( It is also possible to use a commercial product such as a product manufactured by Co., Ltd.

  The content (blending amount) of the curing accelerator (H) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the compounds having a cyclic ether structure contained in the curable epoxy resin composition is 100 parts by weight. The amount is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, and still more preferably 0.03 to 2 parts by weight. By setting the content of the curing accelerator (H) to 0.01 parts by weight or more, a more efficient curing promoting effect tends to be obtained. On the other hand, by setting the content of the curing accelerator (H) to 5 parts by weight or less, there is a tendency that coloring is further suppressed and a cured product excellent in hue is obtained.

[Additive]
In addition to the above, the curable epoxy resin composition of the present invention may contain various additives within a range that does not impair the effects of the present invention. For example, when a compound having a hydroxy group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained as the additive, the reaction can be allowed to proceed slowly. Other silane coupling agents such as silicone-based and fluorine-based antifoaming agents, leveling agents, and γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, as long as the viscosity and transparency are not impaired. , Surfactants, inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors (eg YAG phosphor fine particles, silicate phosphors) Conventional additives such as inorganic phosphor fine particles such as fine particles), release agents, antioxidants other than the antioxidant (D) (for example, sulfur-based antioxidants, hindered amine-based antioxidants, etc.) are used. be able to. The content (blending amount) of the additive in the curable epoxy resin composition of the present invention is not particularly limited. For example, in the range of 0 to 20% by weight with respect to the curable epoxy resin composition (100% by weight). It can be selected appropriately.

  The curable epoxy resin composition of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components in a heated state as necessary. In addition, the curable epoxy resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more stored separately. These components can also be used as a multi-liquid composition (for example, a two-liquid system) that is used by mixing them at a predetermined ratio before use. The stirring / mixing method is not particularly limited, and for example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.

<Hardened product>
By curing the curable epoxy resin composition of the present invention, it is excellent in durability against high-temperature heat and thermal shock, and has high adhesion and adhesion strength to an adherend, and is particularly used as a sealing material for optical semiconductor elements. Thus, a cured product capable of improving the current-carrying characteristics, moisture absorption reflow resistance, and thermal shock resistance of the optical semiconductor device (the cured product obtained by curing the curable epoxy resin composition of the present invention is referred to as “the present invention. May be referred to as a “cured product”. As the curing means, known or conventional means such as heat treatment or light irradiation treatment can be used. Although the temperature (curing temperature) at the time of making it harden | cure by heating is not specifically limited, 45-200 degreeC is preferable, More preferably, it is 50-190 degreeC, More preferably, it is 55-180 degreeC. In addition, the heating time (curing time) for curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit value in the above range, curing is insufficient. On the contrary, when the curing temperature and the curing time are higher than the upper limit value in the above range, the resin component may be decomposed. Although the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased. Moreover, hardening can also be performed in one step and can also be performed in two or more steps.

<Resin composition for optical semiconductor encapsulation>
The curable epoxy resin composition of the present invention is a resin composition for sealing an optical semiconductor element in an optical semiconductor device, that is, an optical semiconductor sealing resin composition (an optical semiconductor element sealing agent in an optical semiconductor device). ) Can be preferably used. By using the curable epoxy resin composition of the present invention as a resin composition for encapsulating an optical semiconductor, it is excellent in durability against high-temperature heat and thermal shock, and is cured by a cured product having high adhesion to an adherend and high adhesive strength. An optical semiconductor device in which the semiconductor element is sealed is obtained. The optical semiconductor device is excellent in current-carrying characteristics at high temperatures, moisture absorption reflow resistance, and thermal shock resistance, and has high quality and durability.

<Optical semiconductor device>
The optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition (resin composition for optical semiconductor sealing) of the present invention. The optical semiconductor element can be sealed, for example, by injecting the curable epoxy resin composition prepared by the above-described method into a predetermined mold and heat-curing under predetermined conditions. Thereby, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the curable epoxy resin composition is obtained. The curing temperature and the curing time can be appropriately set within the same range as when the cured product is prepared.

  The curable epoxy resin composition of the present invention is not limited to the above-described optical semiconductor element sealing application (sealing agent), for example, a semiconductor element sealing application (sealing agent) other than an optical semiconductor element, adhesion Agent, electrical insulating material, laminate, coating, ink, paint, sealant, resist, composite material, transparent substrate, transparent sheet, transparent film, optical element, optical lens, optical member, stereolithography, electronic paper, touch panel, solar It can be used for various applications such as battery substrates, optical waveguides, light guide plates, and holographic memories.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, "-" in Tables 1 and 2 means that the component was not blended.

Example 1
First, in the blending ratio (unit: parts by weight) shown in Table 1, the trade name “Celoxide 2021P” (manufactured by Daicel Corporation), the trade name “ESREC B BL-1H” (manufactured by Sekisui Chemical Co., Ltd.), and The product name “ADK STAB AO-60” (manufactured by ADEKA Corporation) is uniformly applied using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinkey Corporation, the same shall apply hereinafter). Mixed. In addition, the said mixing was implemented by stirring at 80 degreeC for 1 hour. After cooling, the product name “Aron Oxetane OXT-101” (manufactured by Toagosei Co., Ltd.) and the product name “Sun-Aid SI-100L” (curing catalyst, manufactured by Sanshin Chemical Industry Co., Ltd.) are added, and revolving stirring Using a device, the mixture was uniformly mixed and defoamed to produce a curable epoxy resin composition.
Further, the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1, and then in an oven (resin curing oven) at 150 ° C. By heating for 2 hours, an optical semiconductor device in which an optical semiconductor element was sealed with a cured product of the curable epoxy resin composition was produced. In FIG. 1, 100 is a reflector (light reflecting resin composition), 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, 104 is a cured product (sealing material), and 105 is an adhesive (diameter). Touch paste material).

Examples 2-8, Comparative Examples 1-5
A curable epoxy resin composition was produced in the same manner as in Example 1 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 1. In Examples 6 to 8, the isocyanuric acid derivative (E) was blended at 80 ° C. for 1 hour.
Further, an optical semiconductor device was manufactured in the same manner as in Example 1.

Production Example 1
(Production of curing agent composition (K agent))
In the blending ratio (unit: parts by weight) shown in Table 2, the trade name “Licacid MH-700F” (curing agent, manufactured by Shin Nippon Rika Co., Ltd.), the trade name “U-CAT 18X” (curing accelerator, San Apro ( Co., Ltd.) and ethylene glycol (additive, manufactured by Wako Pure Chemical Industries, Ltd.) are uniformly mixed using a self-revolving stirrer, defoamed, and a curing agent composition (“K agent”). In some cases).

Example 9
First, in the compounding ratio (unit: parts by weight) shown in Table 2, the trade name “Celoxide 2021P” (manufactured by Daicel Corporation), the trade name “ESREC B BL-1H” (manufactured by Sekisui Chemical Co., Ltd.), and The product name “ADK STAB AO-60” (manufactured by ADEKA Corporation) was mixed uniformly using a self-revolving stirrer. In addition, the said mixing was implemented by stirring at 80 degreeC for 1 hour. After cooling, a trade name “Aron Oxetane OXT-101” (manufactured by Toagosei Co., Ltd.) was added, and the mixture was uniformly mixed using a self-revolving stirrer and defoamed to produce a mixture.
Next, the revolution mixture stirrer is used for the mixture obtained above and the curing agent composition (K agent) obtained in Production Example 1 so that the blending ratio (unit: parts by weight) shown in Table 2 is obtained. Then, the mixture was uniformly mixed and defoamed to produce a curable epoxy resin composition.
Further, the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1, and then in an oven (resin curing oven) at 120 ° C. By heating for 5 hours, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable epoxy resin composition was produced.

Examples 10-16, Comparative Examples 6-10
A curable epoxy resin composition was produced in the same manner as in Example 9 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 2. In Examples 14 to 16, the isocyanuric acid derivative (E) was blended when stirring at 80 ° C. for 1 hour.
Further, an optical semiconductor device was manufactured in the same manner as in Example 9.

<Evaluation>
The following evaluation tests were carried out on the optical semiconductor devices obtained in the examples and comparative examples.

[High temperature energization test]
The total luminous flux of the optical semiconductor devices obtained in the examples and comparative examples was measured using a total luminous flux measuring machine, and this was defined as “total luminous flux for 0 hour”. Further, the total luminous flux after flowing a current of 20 mA through the optical semiconductor device for 100 hours in a constant temperature bath at 85 ° C. was measured, and this was defined as “total luminous flux after 100 hours”. And luminous intensity retention was computed from the following formula. The results are shown in the column of “Luminance retention rate [%]” in Tables 1 and 2.
{Luminance retention (%)}
= {Total luminous flux after 100 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

[Solder heat resistance test]
The optical semiconductor devices obtained in the examples and comparative examples (two used for each curable epoxy resin composition) were allowed to absorb moisture for 168 hours under conditions of 85 ° C. and 60% RH, and then reflow oven And heated under the following heating conditions. Thereafter, the optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then placed in a reflow furnace again and heated under the same conditions. That is, in this test, the thermal history under the following heating conditions was given twice to the optical semiconductor device.
[Heating conditions (based on surface temperature of optical semiconductor device)]
(1) Preheating: 150 to 190 ° C. for 60 to 120 seconds (2) Main heating after preheating: 217 ° C. or more for 60 to 150 seconds, maximum temperature 260 ° C.
However, the rate of temperature increase when shifting from preheating to main heating was controlled to 3 ° C./second at the maximum.
FIG. 2 shows an example of the surface temperature profile of the optical semiconductor device during heating in the reflow furnace (temperature profile in one of the two heating operations).
Next, the optical semiconductor device after the heat treatment was immersed in red ink (aqueous) at 25 ° C. for 1 hour. Thereafter, the digital ink is taken out from the red ink and whether or not the red ink is immersed in the optical semiconductor device (the electrode is dyed red when immersed) is a digital microscope (trade name “VHX-900”, Co., Ltd.). Using Keyence). Of the two optical semiconductor devices, the number of optical semiconductor devices in which red ink is immersed is shown in the column of “Solder heat resistance test [Red ink immersion number]” in Tables 1 and 2.

[Thermal shock test]
The optical semiconductor devices obtained in Examples and Comparative Examples (two used for each curable epoxy resin composition) were exposed in an atmosphere of −40 ° C. for 30 minutes, and then in an atmosphere of 100 ° C. A thermal shock with one cycle of exposure to 30 minutes was applied for 200 cycles using a thermal shock tester.
Then, the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), and cracks with a length of 90 μm or more occurred in the cured product (sealing material). I confirmed it. Of the two optical semiconductor devices, the number of optical semiconductor devices in which a crack having a length of 90 μm or more occurred in the cured product is shown in the column of “thermal shock test [number of cracks]” in Tables 1 and 2.

[Die share test]
A die shear test using the curable epoxy resin compositions obtained in Examples and Comparative Examples was performed according to the following procedure.
A curable epoxy resin composition was applied onto an Ag-plated Cu substrate so that the adhesion area was 1.25 mm × 1.25 mm, and an Si chip was placed thereon. Next, this was heated at 150 degreeC for 2 hours, the curable epoxy resin composition was hardened, and the test sample was produced. With respect to this test sample, the die shear strength at 25 ° C. was evaluated at a speed of 300 μm / second using a die shear tester (trade name “DAGE 4000”, manufactured by Arctec Co., Ltd.). The results are shown in the column of “Die share test [N]” in Tables 1 and 2.

[Comprehensive judgment]
As a result of each test, the case where all of the following (1) to (4) were satisfied was judged as ◯ (good). On the other hand, the case where any one of the following (1) to (4) was not satisfied was determined as x (defective).
(1) High-temperature energization test: luminous intensity retention of 90% or more (2) Solder heat resistance test: No. of optical semiconductor devices immersed in red ink (3) Thermal shock test: Hardened material (encapsulant) The number of optical semiconductor devices in which cracks having a length of 90 μm or more occurred was 0. (4) Die shear test: die shear strength of 20 N or more The results are shown in the “Comprehensive judgment” column of Tables 1 and 2.

In addition, the component used by the Example and the comparative example is as follows.
・ Alicyclic epoxy compounds (A)
Celoxide 2021P: Trade name “Celoxide 2021P” [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate], manufactured by Daicel Corporation, Oxetane compound (B)
OXT-101: Trade name “Aron Oxetane OXT-101” [3-ethyl-3-hydroxymethyloxetane], manufactured by Toagosei Co., Ltd. OXT-221: Trade name “Aron Oxetane OXT-221” [3-ethyl {[ (3-ethyloxetane-3-yl) methoxy] methyl} oxetane], manufactured by Toagosei Co., Ltd., polyvinyl butyral resin (C)
BL-1H: Trade name “ESREC B BL-1H”, manufactured by Sekisui Chemical Co., Ltd., antioxidant (D)
AO-60: trade name "Adeka Stub AO-60", manufactured by ADEKA Corporation HP-10: trade name "Adeka Stub HP-10", manufactured by ADEKA Corporation, isocyanuric acid derivative (E)
TEPIC: trade name “TEPIC” [triglycidyl isocyanurate], manufactured by Nissan Chemical Industries, Ltd. MA-DGIC: trade name “MA-DGIC” [monoallyl diglycidyl isocyanurate], manufactured by Shikoku Kasei Kogyo Co., Ltd. DA- MGIC: Trade name “DA-MGIC” [diallyl monoglycidyl isocyanurate], manufactured by Shikoku Kasei Kogyo Co., Ltd., curing catalyst (F)
Sun-Aid SI-100L: Trade name “Sun-Aid SI-100L”, Sanshin Chemical Industry Co., Ltd., curing agent (G)
MH-700F: Trade name “Licacid MH-700F” [4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30], manufactured by Shin Nippon Rika Co., Ltd., curing accelerator (H)
U-CAT 18X: Product name “U-CAT 18X”, manufactured by San Apro Co., Ltd. Additives Ethylene glycol: manufactured by Wako Pure Chemical Industries, Ltd.

Test equipment ・ Resin curing oven ESPH Co., Ltd. GPH-201
-Thermostatic chamber ESPEC Co., Ltd. Small high temperature chamber ST-120B1
・ Total luminous flux measuring machine Optronic Laboratories Multi-spectral Radiation Measurement System OL771
・ Thermal shock tester Espec Co., Ltd. Small thermal shock device TSE-11-A
-Reflow furnace manufactured by Nippon Antom Co., Ltd., UNI-5016F

100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor element 103: Bonding wire 104: Cured material (sealing material)
105: Adhesive (Die attach paste)

Claims (8)

  Group consisting of alicyclic epoxy compound (A), oxetane compound (B) having one or more oxetane rings in the molecule, polyvinyl butyral resin (C), phosphorus antioxidant and phenolic antioxidant A curable epoxy resin composition comprising at least one antioxidant (D) more selected.   The curable epoxy resin composition according to claim 1, wherein the oxetane compound (B) is an oxetane compound (B1) having one or more hydroxyl groups in the molecule.   Furthermore, the curable epoxy resin composition of Claim 1 or 2 containing the isocyanuric acid derivative (E) which has a 1 or more oxirane ring in a molecule | numerator.   Furthermore, the curable epoxy resin composition of any one of Claims 1-3 containing a curing catalyst (F).   Furthermore, the curable epoxy resin composition of any one of Claims 1-3 containing a hardening | curing agent (G) and a hardening accelerator (H).   Hardened | cured material obtained by hardening the curable epoxy resin composition of any one of Claims 1-5.   It is a resin composition for optical semiconductor sealing, The curable epoxy resin composition of any one of Claims 1-5.   An optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition according to claim 7.

Images